Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/44—Polyester-amides

Definitions

• the present invention relates to a polyamide rheo­logical additive and a solution containing the additive.
• the present invention also relates to a thickened com­position containing the additive.
• organo-modified clay One type of material which has been shown to be useful to thicken various organic compositions is organo-modified clay.
• Exemplary U.S. patents which des­cribe different kinds of organo-modified (otherwise known as organophilic) clays are U.S. Patent Nos. 4,081,496, 4,105,578, 4,116,866, 4,193,806, 4,208,218, 4,216,135, 4,287,086, 4,391,637, 4,410,364, 4,412,018, 4,434,075, 4,434,076, 4,450,095 and 4,517,112.
• rheological additives have been designed to thicken aqueous based compositions.
• Such additives can be based on polyurethanes such as disclosed in U.S. Patent Nos. 4,079,028, 4,155,892, 4,436,862 and 4,499,233.
• U.S. Patent No. 4,462,926 discloses a thixotropising agent for unsaturated polyester resins consisting of at least one cyclohexylamide of a saturated fatty acid which contains at least 10 carbon atoms and one or more oligo­meric ester amides which have an average molecular weight of from 600 to 3,000, a content of carboxylic acid amide groups of from 1.5 to 15% by weight and a content of car­boxylate groups of from 2 to 13% by weight.
• a different type of polyamide thixotropic agent is set forth in U.S. Patent No. 3,131,201 which describes a resinous composition which is the reaction product of an alkyl diamine having from 2 to 6 carbon atoms and two terminal primary amines with a copolymer formed by the reaction of a glyceride of a polyunsaturated fatty acid having an iodine value above 130 and a conjugated ali­cyclic diene hydrocarbon monomer.
• U.S. Patent No. 2,410,788 describes fatty amide polymers which are suitable for modifying the properties of textile fibers.
• the polymers are resinous or semi-resinous materials in which dialcohol substituted carboamido com­pounds carrying side chains containing polyamino acid amide radicals are linked together by reaction with poly­basic acids.
• a polyamide resin binder for printing inks is obtained from a combination of dimerized fatty acids and dimerized rosin acids with an alkylene diamine having from 2 to 6 carbon atoms, preferably ethylene diamine.
• U.S. Patent No. 3,957,733 sets forth an engineer­ing plastic which is a polyamide of a 19 carbon diacid and trimethylhexamethylene diamine.
• U.S. Patent No. 4,062,819 describes poly­amide blends having improved flow characteristics and rheological properties which are formed from a nylon-type polyamide and a minor amount of a polyamide derived from a high molecular weight dibasic acid.
• the second poly­amide is more specifically obtained by the reaction of a long-chain dibasic acid containing 18 or more carbon atoms and a diamine or mixture of diamines.
• the present invention provides an improved rheo­logical additive for organic compositions.
• the additive may be efficient in thickening organic compositions. It can be readily dispersed in the organic composition to be thickened.
• the organic solvent solution of the polyamide rheological additive may be easy to handle and can readily be incorporated in organic compositions.
• the present invention provides a rheological additive which comprises the reaction product of:
• the present invention provides a solution formed by dissolving the polyamide rheological additive in an organic solvent and a thickened organic composition containing the polyamide rheological addi­tive.
• one aspect of the present invention relates to a polyamide rheological additive comprising the reaction product of polycarboxylic acid, active hydrogen compound and monocarboxylic acid capping agent.
• the polycarboxylic acid has at least 5 carbon atoms, preferably from 6 to 36 carbon atoms and most preferably from 16 to 20 carbon atoms per carboxylic acid group. While polycarboxylic acids having more than 2 carboxylic acid groups may be employed, the amount of such acids should be limited to avoid extensive cross-­linking which would render the reaction product insoluble in the intended organic composition. This typically means that less than about 80 percent by weight, prefer­ably less than 20 percent by weight and most preferably less than 5 percent by weight of the total amount of polycarboxylic acid should have three or more carboxylic acid groups.
• Illustrative polycarboxylic acids include sebacic acid, poly(butadiene)dioic acids, dodecane dicarboxylic acid and mixtures thereof.
• Especially preferred poly­carboxylic acids are oligomers of fatty acids having a carbon chain of from 16 to 22 carbon atoms, preferably 16 to 18 carbon atoms.
• Exemplary fatty acids are those derived from soybean oil, castor oil, tall oil, corn oil, cottonseed oil, kapok seed oil, linseed oil and mixtures thereof. Even further preferred are oligomers of fatty acids which are substantially comprised of the dimerized fatty acid.
• the dimerized fatty acid constitutes at least about 20% by weight of the oligomerized fatty acid, preferably at least about 80% by weight and more preferably comprises at least 95% by weight of the oligomerized fatty acid.
• the oligomerized fatty acid preferably also has a low monomer content such as less than about 10% by weight and more preferably less than about 4% by weight.
• oligomerized fatty acid including the described low monomer content oligomer
• suitable oligomerized fatty acids are commercially available such as certain oligomerized fatty acids available under the name Empol from Emery Industries, a division of National Distillers & Chemical Corporation and Sylvadym T-18 available from Arizona Chemical Company.
• the active hydrogen compound has the general formula X m -R-Y n wherein R represents a group containing from 2 to 12 carbon atoms and which may contain non-­reactive groups, such as ether, alkoxy or halogen groups, X and Y are independently selected from primary amino, secondary amino and hydroxyl and m and n are at least 1, the sum of (m + n) is at least 2, and preferively m and n are each 1. Since the presence of amide groups is essential to the present invention, at least 90%, preferably at least 95% and most preferably all of the X and Y groups participating in the reaction are primary amino, secondary amino or a mixture thereof.
• R represents a group containing from 6 to 12 carbon atoms and more preferably R represents a group containing from 6 to 8 carbon atoms.
• the active hydrogen compound can have 3 or more active groups.
• the amount of active hydrogen compound having 3 or more active groups should not be selected such that the reaction product is cross-linked to an extent such that it is insoluble in the environment of the organic composition in which it is to be used.
• Illustrative active hydrogen compounds include polyamines, such as 1,2-diaminoethane, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diamino­hexane, 1,8-diaminooctane, 1,12-diaminododecane, 3,3-­diaminopropyl-N-methylamine, N-alkyl-1,3-diamino­propanes wherein the alkyl group is a long carbon chain such as coco or tallow alkyl, soya alkyl, oleyl, stearyl and mixtures thereof, and amino alcohols, such as ethanolamine, 6-aminohexanol, aminoethylethanolamine and mixtures thereof.
• polyamines such as 1,2-diaminoethane, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,
• Diols which may constitute a portion of the active hydrogen compound are exemplified by 1,2-­ethanediol, 1,2- and 1,3-propane diol, 1,4-butane diol, 1,6-hexanediol, diethylene glycol, triethylene glycol and mixtures thereof.
• the amount of diol must be limited such that of the total active hydrogen groups participating in the reaction, at least 90 mole percent must be primary and/or secondary amino.
• Preferred active hydrogen compounds are diamines, especially diamines having from 6 to 12 carbon atoms with the most preferred diamine being 1,6-­diaminohexane.
• the capping agent is used to terminate the reaction product of the polycarboxylic acid and the active hydrogen compound and is a monocarboxylic acid which is at least one of unsaturated and hydroxylated.
• the monocarboxylic acid generally has from 8 to 22 carbon atoms. While monocarboxylic acids having fewer carbon atoms may be used to achieve certain benefits in environments such as organic solvent-based coatings, such smaller monocarboxylic acid should be limited to less than 20 mole percent, preferably less than 10 mole percent of the total capping agent employed and most preferably are absent.
• the structure of the capping agent has a major impact on the performance of the resulting polyamide of this invention.
• monocar­boxylic acid capping agents which contain unsaturation, especially a single point of unsaturation, such as oleic acid, are found to improve the ultimate efficien­cy of the additive in an organic solvent-based coating composition versus the saturated monocarboxylic acid analog.
• the meaning of the term "ultimate efficiency" is the efficiency of the additive after incorporation into a system under the most optimum conditions for that particular additive.
• Hydroxylated saturated monocarboxylic acids improve the ease of dispersion (incorporation) of the polyamide rheological additive, but reduce its efficiency in an organic solvent-based coating composition.
• incorporation of a polyamide rheological additive which is capped with a hydroxylated monocar­boxylic acid into an organic solvent-based coating composition will require less energy input than for, e.g., a similar polyamide rheological additive capped with an unsaturated and non-hydroxylated monocarboxylic acid.
• a monocarboxylic acid capping agent with a single point of unsaturation (if aliphatic) or a single hydroxyl moiety and even further preferred is a monocarboxylic acid capping agent with a single point of unsaturation (if ali­phatic) and a single hydroxyl moiety.
• the capping agent may also have a straight or branched chain and may also contain groups, such as tertiary amino, alkoxy, halo, keto, etc., which do not react with the other components used to prepare the rheological additive.
• Illustrative unsaturated aliphatic acids include linoleic acid, linolenic acid, oleic acid, monocarboxylic acids derived from dehydrated castor oil, undecylenic acid, tall oil fatty acids, soya fatty acids, and mixtures thereof.
• Aromatic acids, such as benzoic acid, salicylic acid and mixtures thereof may also be employed as a portion of the total capping agent.
• Hydroxylated monocarboxylic acids include ricinoleic acid, 12-hydroxystearic acid, 12-hydroxy­dodecanoic acid, and mixtures thereof.
• the most preferred capping agent is ricinoleic acid.
• a portion of the capping agent may be composed of a compound which is not a monocarboxylic acid which is unsaturated and/or hydroxylated.
• a portion of the capping agent may be composed of at least one non-hydroxylated, saturated aliphatic monocarboxylic acid such as octanoic acid, nonanoic acid, dodecanoic acid, octadecanoic acid, docosanoic acid, hydrogenated tallow acids, stearic acid and mixtures thereof.
• the described monocar­boxylic acid capping agent at least about 25 mole percent, preferably at least about 50 mole percent and most preferably at least about 90 mole percent of the capping agent actually reacted should be the described unsaturated and/or hydroxylated monocarboxylic acid.
• an especially preferred aspect of the present invention is a polyamide rheological additive which is the reaction product of oligomer of fatty acid having a carbon chain of from 16 to 18 carbon atoms, diamine having from 6 to 12 carbon atoms and un­saturated and hydroxylated monocarboxylic acid having from 16 to 22 carbon atoms as capping agent with the most preferred capping agent being ricinoleic acid.
• the reaction product consists essentially of the defined components.
• the specific types and amounts of the reactants are selected so as to obtain a nonresinous reaction product which can be dispersed in the intended organic composition and which will function as a rheological additive.
• the amount of active hydrogen compound reacted to form the reaction product is in the range of from about 1.0 to about 4.0, preferably from about 1.0 to about 3.0 and most preferably from about 1.0 to about 2.0 moles per mole of the reacted polycarboxylic acid.
• the amount of capping agent selected is sufficient to cap the active hydrogen compound ends of the reaction product of the polycarboxylic acid and the active hydrogen compound.
• the amount of the capping agent reacted to form the reaction product is in the range of from about 0.1 to about 4.0, preferably from about 0.17 to about 2.0 and most preferably from about 0.3 to about 2.0 moles per mole of the reacted polycarboxylic acid.
• the molar amounts of the components in the reaction mixture may be different than that of the formed polyamide rheological additive. That is, one or more of the reactants may be employed in excess. Typically, for instance, it has been found advantageous to use a 2-10% molar excess of the active hydrogen compound (e.g., diamine) which accelerates the reaction and makes up for that lost by co-distillation with the water of reaction.
• the average molecular weight of the reaction product ranges from about 500 to about 12,000, preferably from about 1,250 to about 8,500 and most preferably from about 1,250 to about 4,000. It can therefore be understood from this discussion that the polyamide rheological additive is not a polymeric resin, but is instead a relatively low molecular weight compound.
• the polyamide rheological additive may be prepared according to known techniques.
• the reactants may be charged to a suitable reaction vessel which is equipped with a mechanical stirrer, a thermometer, a Dean-Stark trap-Bartlett modification and a nitrogen inlet.
• the vessel can be heated with stirring under a nitrogen blanket.
• acid number e.g., preferably less than about 4
• the polyamide is cooled and is discharged. If amenable to grinding, the polyamide can then be ground to a fine particle size.
• the degree of particle size reduction required or preferred is dependent on the particular polyamide rheological additive composition, or more properly, on the melting point of the particular polyamide composi­tion, with the harder, higher melting polyamide compositions requiring a finer particle size in order to achieve a satisfactory degree of dispersion of the rheological additive in the application in which it is employed.
• a preferred general formula can be set forth as follows: R ⁇ -C(O)-X-R-Y-[-C(O)-R ⁇ -C(O)-X-R-Y-] x -C(O)R ⁇ wherein R ⁇ is the residue of the monocarboxylic acid capping agent, R represents a group containing from 2 to 12 carbon atoms, X and Y are the residues of primary amino, secondary amino or hydroxyl groups, R ⁇ is the residue of the polycarboxylic acid, and x is from 1 to 17, preferably from 1 to 12 and most preferably is from 1 to 5.
• the polyamide rheological additives of the present invention are a marked advance in the art.
• the polyamide rheological additives of the present invention can have excellent flow and levelling properties, as well as excellent efficiency and dispersing characteristics.
• coating compositions containing the polyamide rheological additives of the present inven­tion may be prepared such that large agglomerates (sometimes referred to as "seeds") which sometimes form on storage of coating compositions containing prior art thixotropes can be avoided.
• the polyamide rheological additive of the present invention may be used to thicken a variety of organic solvent-based compositions and it is believed that the rheological additive can also be used in some solvent-free compositions.
• the additive is particular­ly useful, for example, in thickening aliphatic and aromatic solvent-based compositions and, while not as efficient, may also be used in certain moderately polar (e.g., ketones and alcohols) based compositions.
• Illustrative organic solvent-based compositions include aliphatic alkyd paints such as Trade Sales solvent-­based paints and varnishes; aromatic solvent-based paints based on acrylic, alkyd and polyester binders, such as standard quality industrial paints which include appliance enamels, equipment enamels, and automotive refinish enamels; and certain sealants.
• a useful screening test is to dissolve the rheological additive in xylene in an amount of 10% by weight at 60°C to determine if a non-pourable, clear or slightly cloudy gel forms upon cooling to room temperature. Such gel formation is indicative of an acceptable polyamide rheological additive.
• the amount of polyamide rheological additive used in a specific instance is determined by numerous factors including the reactants used in the preparation of the additive, the type of organic solvent-based composition to be thickened and the level of thickening desired. However, a general range is from about 1.5 to about 30 pounds per hundred gallons of composition. On a weight basis, the amount of polyamide rheological additive is generally from about 0.1 to about 5% by weight, preferably from about 0.1 to about 3% by weight and most preferably from about 0.2 to about 1% by weight.
• the polyamide can be first pre-dispersed in a compatible organic solvent, especially at a slightly elevated temperature.
• the solvent contains at least about 10% by weight of an alcohol and preferably contains at least about 25% by weight of an alcohol.
• Representative alcohols include methanol, ethanol, 1-­propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, isoamyl alcohol, and mixtures thereof with the pre­ferred alcohol being 2-propanol.
• the function of the alcohol solvent is to hydrogen bond with the polyamide, which interaction negates or substantially reduces the intermolecular polyamide-polyamide interactions.
• the concentration of the alcohol is so small that it is ineffective in substantially reducing the interactions of the polyamide with itself or with other components of the system.
• the amount of groups participating in the reaction from the active hydrogen compound can be reduced from 90% amino to at least 50% amino groups.
• the remaining portion of the solvent can be any organic solvent, which, with the alcohol, will provide a fluid solution of the polyamide rheological additive and which will be compatible with the intended application of the additive.
• Preferred cosolvents are aromatic solvents, such as benzene, toluene, xylenes, ethyl benzene, naphthalene-containing solvents and mixtures thereof, and aliphatic solvents such as mineral spirits, mineral oil, hexanes, heptanes and mixtures thereof, with the most preferred cosolvents being toluene and xylenes.
• the preferred combination of solvents is 2-­propanol and toluene in a weight ratio of from about 1:1 to about 1:9 and most preferably from about 1:1 to 1:4.
• Such a combination provides a solution which remains fluid on storage at ambient temperatures and functions as an efficient rheological additive (thixo­trope) when used in an organic solvent based applica­tion.
• the amount of polyamide rheological additive which can be pre-dispersed in the solvent understandably varies depending on several factors, but generally is in the range of from about 5 to about 75% by weight, preferably from about 25 to about 50% by weight.
• a one liter resin flask, equipped with a mechanical stirrer, a thermometer, a Dean-Stark trap­Bartlett modification and a nitrogen inlet is charged with molten or liquid active hydrogen compound, polycarboxylic acid and capping agent.
• the mixture is heated with stirring under a nitrogen blanket.
• Water begins to be evolved at approximately 150-155°C. After 2 hours at 180-195°C, aliquots are removed hourly and analyzed for acid number and the reaction is continued until the acid number reaches a minimum or falls below 4.
• the reaction product is cooled to 140-145°C and is discharged into a stainless steel tray and allowed to cool overnight.
• the product is then diced and ground to a fine powder using a Waring Blendor, if amenable to grinding. Depending on the melting point of the reaction product, it may be further ground using a jet mill and the fine particle size product isolated by sieving prior to analysis.
• the preparation and components of the aliphatic gloss enamel are as follows: Stir at 3000 rpm using a Premier Dispermat fitted with a 1-5/8 ⁇ Cowles sawtooth blade. Add: Grind at 5400 rpm using the above described mixer for 15 minutes while maintaining the temperature at 150°F. Cool the paint to 135°F and mix at 2000 rpm while adding the following: 1266 M70 Alkyd Resin is available from NL Chemicals, Inc. Mineral Spirits 66/3 is a Rule 66 compliant mineral spirits, available from Ashland Chemical Company, Industrial Chemicals and Solvents Division. 2101 Titanium Dioxide pigment is available from NL Chemicals, Inc. The Nuxtra driers are available from Nuodex, Inc. Exkin 2 Antiskinning Agent is available from Nuodex, Inc.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyamides (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Paints Or Removers (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

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• 1986
  • 1986-12-09 US US06/939,685 patent/US4778843A/en not_active Expired - Lifetime
• 1987
  • 1987-11-26 ZA ZA878879A patent/ZA878879B/xx unknown
  • 1987-11-27 FI FI875240A patent/FI875240A/fi not_active Application Discontinuation
  • 1987-11-30 CA CA000553144A patent/CA1292341C/en not_active Expired - Fee Related
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  • 1987-12-01 DE DE3752028T patent/DE3752028D1/de not_active Expired - Lifetime
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  • 1987-12-07 JP JP62307799A patent/JP2509957B2/ja not_active Expired - Lifetime
  • 1987-12-08 DK DK643487A patent/DK643487A/da not_active Application Discontinuation
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